Cyano Anthranilamide Insecticides

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I can be used as agrochemical active ingredients and can be prepared in a manner known per se.

The present invention relates to novel anthranilamide derivatives, toprocesses for their preparation, to compositions comprising thosecompounds, and to their use for controlling insects or representativesof the order Acarina.

Anthranilamide derivatives with insecticidal properties are known anddescribed, for example, in WO 04/067528. There have now been found novelcyano-substituted anthranilamide derivatives with pesticidal properties,especially for the control of insects and members of the order Acarina.

The present invention accordingly relates to compounds of formula I

wherein

each of E and Z, which may be the same or different, represents oxygenor sulfur;

A is C₁-C₆alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene, or a bivalentthree- to ten-membered monocyclic or fused bicyclic ring system whichcan be partially saturated or fully saturated and can contain 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms;

and it being possible for the three- to ten-membered ring system itselfand also for the C₁-C₆alkylene, C₂-C₆alkenylene and C₂-C₆alkynylenegroups to be mono-, di- or trisubstituted by halogen, cyano, nitro,hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl, or by

a three- to ten-membered monocyclic or fused bicyclic ring system whichcan be aromatic, partially saturated or fully saturated and can contain1 to 4 hetero atoms selected from the group consisting of nitrogen,oxygen and sulfur, it not being possible for each ring system to containmore than 2 oxygen atoms and more than 2 sulfur atoms, and it beingpossible for the three- to ten-membered ring system itself to be mono-,di- or trisubstituted by halogen, cyano, nitro, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl,C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen;

X is oxygen, NH or C₁-C₄alkyl-N;

Y is a three- to ten-membered monocyclic or fused bicyclic ring systemwhich can be partially saturated or fully saturated and can contain 1 to4 hetero atoms selected from the group consisting of nitrogen, oxygenand sulfur, it not being possible for each ring system to contain morethan 2 oxygen atoms and more than 2 sulfur atoms;

and it being possible for the three- to ten-membered ring system itselfto be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl, or by a three- toten-membered monocyclic or fused bicyclic ring system which can bearomatic, partially saturated or fully saturated and can contain 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms, and it being possible forthe three- to ten-membered ring system itself to be mono-, di- ortrisubstituted by halogen, cyano, nitro, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl,C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C₄alkoxycarbonyl-C₁-C₃-alkylthio, cyano-C₁-C₃alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,N,N-di(C₁-C₂alkyl)amino-sulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen;

p is 0 or 1;

q is 0 or 1;

B is a three- to four-membered ring system which is fully or partiallysaturated and can contain a hetero atom selected from the groupconsisting of nitrogen, oxygen and sulfur, and it being possible for thethree- to four-membered ring system itself to be mono-, di- ortrisubstituted by halogen, cyano, nitro, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl,C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl, or by a three- toten-membered monocyclic or fused bicyclic ring system which can bearomatic, partially saturated or fully saturated and can contain 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms, and it being possible forthe three- to ten-membered ring system itself to be mono-, di- ortrisubstituted by halogen, cyano, nitro, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl,C₅-C₈cycloalkynyl, C_(C) ₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenlthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆halo-alkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylamino-sulfonyl,N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen;

each R₁ independently is halogen, nitro, cyano, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl,C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino,C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy orC₃-C₆trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl orphenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl,C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₁-C₆cycloalkylamino,C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy orC₃-C₆trialkylsilyl;

n is 0, 1, 2 or 3;

each of R₂ and R₃, which may be the same or different, representshydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl; orC₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl substituted byone or more substituents selected from halogen nitro, cyano, hydroxy,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino andC₁-C₆alkyl-C₃-C₆cycloalkylamino;

D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl,3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

or D is a group

R₄, R₄′, R₁₀, R₁₇, and R₁₉ independently from each other, are hydrogen,C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

R₅, R₆, R₈, R₁₁, R₁₂, R₁₅, R₁₆ and R₁₈ independently from each other,are C₁-C₆alkyl mono-, di- or trisubstituted by halogen, cyano, nitro,hydroxy, C₁-C₄alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino or C₃-C₆cycloalkylamino; or are phenyl, 2-pyridyl,3-pyridyl, 4-pyridyl; or are or phenyl, 2-pyridyl, 3-pyridyl or4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy,C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C_(C)₄haloalkylsulfonyl;

R₇, R₉, R₁₃ and R₁₄ independently from each other, are hydrogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkenylor C₃-C₆haloalkenyl and agronomically acceptablesalts/isomers/enantiomers/tautomers/N-oxides of those compounds.

Compounds I which have at least one basic centre can form, for example,acid addition salts, for example with strong inorganic acids such asmineral acids, for example perchloric acid, sulfuric acid, nitric acid,nitrose acid, a phosphorus acid or a hydrohalic acid, with strongorganic carboxylic acids, such as C₁-C₄alkanecarboxylic acids which areunsubstituted or substituted, for example by halogen, for example aceticacid, such as saturated or unsaturated dicarboxylic acids, for exampleoxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid orphthalic acid, such as hydroxycarboxylic acids, for example ascorbicacid, lactic acid, malic acid, tartaric acid or citric acid, or such asbenzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- orarylsulfonic acids which are unsubstituted or substituted, for exampleby halogen, for example methane- or p-toluenesulfonic acid. Compounds Iwhich have at least one acidic group can form, for example, salts withbases, for example mineral salts such as alkali metal or alkaline earthmetal salts, for example sodium, potassium or magnesium salts, or saltswith ammonia or an organic amine, such as morpholine, piperidine,pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-,diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- ortrihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.Where appropriate, the corresponding internal salts can furthermore beformed. Preferred within the scope of the invention are agrochemicallyadvantageous salts; however, the invention also encompasses salts whichhave disadvantage for agrochemical use, for example salts which are tobees or fish, and which are employed, for example, for the isolation orpurification of free compounds I or agrochemically utilizable saltsthereof. Owing to the close relationship between the compounds I in freeform and in the form of their salts, for the purposes of the inventionthe free compounds I or their salts hereinabove and hereinbelow arerespectively to be understood as including, where appropriate, thecorresponding salts or the free compounds I. The same appliesanalogously to tautomers of compounds I and salts thereof. In general,the free form is preferred in each case.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl andalkynyl radicals are derived from the alkyl radicals mentioned. Thealkenyl and alkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Suitable haloalkenyl groups are alkenyl groups which are mono- orpolysubstituted by halogen, halogen being fluorine, chlorine, bromineand iodine and in particular fluorine and chlorine, for example2,2-difluoro-1 -methylvinyl, 3-fluoropropenyl, 3-chloropropenyl,3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and4,4,4-trifluorobut-2-en-1-yl. Among the C₃-C₂₀alkenyl groups which aremono-, di- or trisubstituted by halogen, preference is given to thosehaving a chain length of from 3 to 5 carbon atoms.

Suitable haloalkynyl groups are, for example, alkynyl groups which aremono- or polysubstituted by halogen, halogen being bromine, iodine andin particular fluorine and chlorine, for example 3-fluoropropynyl,3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro-propynyl and4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono-or polysubstituted by halogen, preference is given to those having achain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl,isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferablymethoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have achain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example,fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy,2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferablydifluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groupspreferably have a chain length of from 1 to 6 carbon atoms. Alkylthiois, for example, methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferablymethylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl,ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl,isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferablymethylsulfinyl and ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl orethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length offrom 1 to 8 carbon atoms. Examples of alkoxyalkoxy groups are:methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy,ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, forexample, methylamino, ethylamino, n-propylamino, isopropylamino or theisomeric butylamines. Dialkylamino is, for example, dimethylamino,methylethylamino, diethylamino, n-propylmethylamino, dibutylamino anddiisopropylamino. Preference is given to alkylamino groups having achain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferablyhave a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl,n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkylgroups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, forexample, methylthiomethyl, methylthioethyl, ethylthiomethyl,ethylthioethyl, n-propylthiomethyl, n-propylthioethyl,isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethylor butylthiobutyl. The cycloalkyl groups preferably have from 3 to 6ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl. Phenyl, also as part of a substituent such as phenoxy,benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, maybe substituted. In this case, the substituents can be in ortho, metaand/or para position. The preferred substituent positions are the orthoand para positions to the ring attachment point.

Examples for B as a optionally substituted three- to four-membered ringsystem which is fully or partially saturated and can contain a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur,are cyclopropyl, methyl-cyclopropyl, cyclopropenyl, cyclobutyl,cyclobutenyl,

According to the present invention, a three- to ten-membered, monocyclicor fused bicyclic ring system which may be partially saturated or fullysaturated is, depending of the number of ring members, for example,selected from the group consisting of

cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where saidcycloalkylgroups for their part may be preferably unsubstituted orsubstituted by C₁-C₆alkyl or halogen, or is

wherein each R₂₆ is methyl, each R₂₇ and each R₂₈ are independentlyhydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl, X₄is oxygen or sulfur and r=1, 2, 3 or 4.

Where no free valency is indicated in those definitions, for example asin

the linkage site is located at the carbon atom labelled “CH” or in acase such as, for example,

at the bonding site indicated at the bottom left. The second valence forthe bivalent ring system of substituent A or Y can be located at anysuitable position of the ring.

According to the present invention, a three- to ten-membered monocyclicor fused bicyclic ring system which may be aromatic, partially saturatedor fully saturated is, depending of the number of ring members, forexample, selected from the group consisting of

cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where saidcycloalkylgroups for their part may be preferably unsubstituted orsubstituted by C₁-C₆alkyl or halogen, or is phenyl, benzyl, naphthyl orthe following heterocyclic groups: pyrrolyl; pyridyl; pyrazolyl;pyrimidyl; pyrazinyl; imidazolyl; thiadiazolyl; quinazolinyl; furyl;oxadiazolyl; indolizinyl; pyranyl; isobenzofuranyl; thienyl;naphthyridinyl; (1-methyl-1H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3-yl)-;(1-propyl-1H-pyrazol-3-yl)-; (1H-pyrazol-3-yl)-;(1,5-dimethyl-1H-pyrazol-3-yl)-; (4-chloro-1-methyl-1H-pyrazol-3-yl)-;(1H-pyrazol-1-yl)-; (3-methyl-1H-pyrazol-1-yl)-;(3,5-dimethyl-1H-pyrazol-1-yl)-; (3-isoxazolyl)-;(5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isox-azolyl)-;(1H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1H-pyrrol-1-yl)-;(1-methyl-1H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2-furanyl)-;(3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3thienyl)-;(1-methyl-1H-imidazol-2-yl)-; (1H-imidazol-2-yl)-;(1-methyl-1H-imidazol-4-yl)-; (1methyl-1H-imidazol-5-yl)-;(4-methyl-2-oxazolyl)-; (5-methyl-2-oxazolyl)-; (2-oxazolyl)-;(2-methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-;(5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5-thiazolyl)-;(2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-;(3-methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-;(1-methyl-1H-1,2,3-triazol-4-yl)-; (2-methyl-2H-1,2,3-triazol-4-yl)-;(4-methyl-2H-1,2,3-triazol-2-yl)-; (1-methyl-1H-1,2,4-triazol-3-yl)-;(1,5-dimethyl-1H-1,2,4-triazol-3-yl)-;(3-methyl-1H-1,2,4-triazol-1-yl)-; (5-methyl-1H-1,2,4-triazol-1-yl)-;(4,5-dimethyl-4H-1,2,4-triazol-3-yl)-;(4-methyl-4H-1,2,4-triazol-3-yl)-; (4H-1,2,4-oxadiazol-5-yl)-;(5-methyl-1,2,3-oxadiazol-4-yl)-; (1,2,3-oxadiazol-4-yl)-;(3-methyl-1,2,4-oxadiazol-a5-yl)-; (5-methyl-1,2,4-oxadiazol-3-yl)-;(4-methyl-3-furazanyl)-; (3-furazanyl)-;(5-methyl-1,2,4-oxadiazol-2-yl)-; (5-methyl-1,2,3-thiadiazol-4-yl)-;(1,2,3-thiadiazol-4-yl)-; (3-methyl-1,2,4-thiadiazol-5-yl)-;(5-methyl-1,2,4-thiadiazol-3-yl)-; (4-methyl-1,2,5-thiadiazol-3-yl)-;(5-methyl-1,3,4-thiadiazol-2-yl)-; (1-methyl-1H-tetrazol-5-yl)-;(1H-tetrazol-5-yl)-; (5-methyl-1H-tetrazol-1-yl)-;(2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-;(5-methyl-2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-;(4-pyridyl)-; (3-pyridyl)-; (6-methyl-3-pyridazinyl)-;(5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-;(4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)-;(2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-;(2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-;(2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyr-azinyl)-; (2-pyrazinyl)-;(4,6-dimethyl-1,3,5-triazin-2-yl)-; (4,6-dichloro-1,3,5-triazin-2-yl)-;(1,3,5-triazin-2-yl)-; (4-methyl-1,3,5-triazin-2-yl)-;(3-methyl-1,2,4-triazin-5-yl)-; (3-methyl-1,2,4-triazin-6-yl)-;

wherein each R₂₆ is methyl, each R₂₇ and each R₂₈ are independentlyhydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl, X₄is oxygen or sulfur and r=1, 2, 3 or 4.

Where no free valency is indicated in those definitions, for example asin

the linkage site is located at the carbon atom labelled “CH” or in acase such as, for example,

at the bonding site indicated at the bottom left.

Preference is given to subgroups of compounds of formula I wherein

a) p and/or q is 0;

b) E and/or Z is oxygen; and/or

c) R₂ and/or R₃ is hydrogen and/or

d) A is a bivalent three- to six-membered saturated monocyclic ringsystem.

X is preferably oxygen, NH; N-Methyl or N-Ethyl.

Y is preferably C₃-C₆cycloalkyl, especially cyclopropyl.

R₄′ is preferably hydrogen.

Special mention should be made of compounds of formula I wherein R₁isselected from C₁-C₄alkyl, halogen, C₁-C₅haloalkyl, nitro, C₁-C₄alkoxy,C₁-C₄-haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl andC₁-C₄haloalkylsulfonyl, in particular from halogen and C₁-C₆alkyl,preferably selected from methyl and halogen, most preferably selectedfrom methyl and chloro, and n is 1 or 2, preferably 1. Preferredposition of R₁ is meta to the group —C(Z)-N(R₃)-A-X—Y—B.

An outstanding group of compounds of formula I comprises those compoundswherein A is C₁-C₆alkylene which may be substituted by C₃-C₆cycloalkyl,C₂-C₆alkenyl, cyano, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₁-C₄alkoxy,halogen or C₁-C₆haloalkyl; or A is C₃-C₆cycloalkylene. Preferably A isC₃-C₆cycloalkylene, most preferably cyclopropylene.

In preferred compounds of formula I, B is cyclopropyl, oxetanyl orcyclobutyl, preferably cyclopropyl.

Special emphasis should also be given to compounds of formula I whereinD is a group D₁, wherein R₅ is 2-pyridyl which can be substituted byhalogen, preferably which is monosubstituted by chloro at the 3-positionof the pyridine ring and R₄ is halogen preferably chloro or bromo,C₁-C₆haloalkyl, C₁-C₄haloalkoxy most preferably 2,2,2-trifluoroethoxy,preferably C₁-C₆haloalkyl, most preferably trifluoromethyl.

Preference is also given to compounds of formula I wherein in particularB is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstitutedby halogen, C₁-C₄alkyl, hydroxy, cyano, C₁-C₄alkoxy or C₁-C₄alkylthio;or B is CH(CH₂O), CH(CHMeO), CH—(CMe₂O), CH(CH₂S), CH(CH₂OCH₂),CH(CHMeOCH₂), CH(CMe₂OCH₂), CH(CH₂S—(O)₂CH₂), CH(CHMeS(O)₂CH₂),CH(CMe₂S(O)₂CH₂), C(Me)-(CH₂O), C(Me)(CHMeO), C(Me)-(CMe₂O),C(Me)-(CH₂S), C(Me)-(CH₂OCH₂), C(Me)(CHMeOCH₂), C(Me)-(CMe₂OCH₂),C(Me)-(CH₂S(O)₂CH₂), C(Me)-(CHMe-S(O)₂CH₂) or C(Me)-(CMe₂-S(O)₂CH₂). Inespecially preferred compounds of formula I B is cyclopropyl orcyclobutyl which may be substituted by halogen or methyl, in particularby chloro, bromo or methyl; most preferably B is cyclopropyl.

The process according to the invention for preparing compounds of theformula I is carried out analogously to known processes, for examplethose described in WO 01/70671, WO 03/016284, WO 03/015518 WO 04/033468and WO 04/067528.

The process for the preparation of a compound of the formula I or, whereappropriate, a tautomer thereof, in each case in free form or in saltform, comprises, for example,

a) to prepare a compound of the formula I, in which R₂ is hydrogen and Eand Z are oxygen, or, where appropriate, a tautomer and/or salt thereof,by reacting a compound of the formula

in which R₁, n, and D have the meanings given for the formula I, or,where appropriate, a tautomer and/or salt thereof with a compound of theformula

HN(R₃)-(A)_(q)-(X)_(p)—Y—B   (III),

in which R₃, p, q, A, X, Y and B have the meanings given for the formulaI, or, where appropriate, with a tautomer and/or salt thereof or,

b) to prepare a compound of the formula I, or, where appropriate, atautomer and/or salt thereof, reacting a compound of the formula

in which R₁, R₂, n, Z and D have the meanings given for the formula I;and X₁is a leaving group,or, where appropriate, a tautomer and/or saltthereof with a compound of the formula

HN(R₃)-(A)_(q)-(X)_(p)—Y—B   (III),

in which R₃, p, q, A, X, Y and B have the meanings given for the formulaI, or, where appropriate, with a tautomer and/or salt thereof or,

c) to prepare a compound of the formula I, or, where appropriate, atautomer and/or salt thereof, by reacting a compound of the formula

in which R₁, R₂, R₃, n, p, q, A, X, Y, Z and B have the meanings givenfor the formula I, or, where appropriate, a tautomer and/or salt thereofwith a compound of the formula

X₂C(═O)D   (VI),

in which R₁has the meaning given for the formula I; and X₂ is a leavinggroup, or, where appropriate, with a tautomer and/or salt thereof and/orconverting a compound of the formula I or, where appropriate, a tautomerthereof, in each case in free form or in salt form, into anothercompound of the formula I or, where appropriate, a tautomer thereof,separating an isomer mixture, which can be obtained in accordance withthe process, and isolating the desired isomer and/or converting a freecompound of the formula I or, where appropriate, a tautomer thereof intoa salt or a salt of a compound of the formula I or, where appropriate, atautomer thereof into the free compound of the formula I or, whereappropriate, a tautomer thereof or into another salt.

The compounds of formula II are novel and are especially developed forthe preparation of the compounds of formula I according to the presentinvention. The compounds of formula II therefore constitute a furtherobject of the present invention. The compounds of formula II can beprepared analogously to the methods described in WO 04/111030.

The compounds of formula V are also novel and are especially developedfor the preparation of the compounds of formula I according to thepresent invention. The compounds of formula V therefore constitute afurther object of the present invention. Compounds of formula V arepreferred, wherein

R₁is C₁-C₄alkyl, halogen, C₁-C₅haloalkyl, nitro, C₁-C₄alkoxy,C₁-C₄-haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl;

R₂ and R₃ are hydrogen;

A is C₁-C₆alkylene which may be substituted by C₃-C₆cycloalkyl,C₂-C₆alkenyl, cyano, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₁-C₄alkoxy,halogen or C₁-C₆haloalkyl; or A is C₃-C₆cycloalkylene;

p and q are, independently from each other, 0 or 1;

X is oxygen, NH; NCH₃ or NC₂H₅;

Y is C₁-C₄alkylene, C₂-C₆alkenylene or C₃-C₆alkinylene or,C₁-C₄alkylene, C₂-C₆alkenylene or C₃-C₆alkinylene substituted byhalogen, C₃-C₆cycloalkyl, C₁-C₄alkylsulfonyl or C₁-C₄alkoxy; and B iscyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted byhalogen, C₁-C₄alkyl, hydroxy, cyano, C₁-C₄alkoxy or C₁-C₄alkylthio; or Bis CH(CH₂O), CH(CHMeO), CH—(CMe₂O), CH(CH₂S), CH(CH₂OCH₂), CH(CHMeOCH₂),CH(CMe₂OCH₂), CH(CH₂S—(O)₂CH₂), CH(CHMeS(O)₂CH₂), CH(CMe₂S(O)₂CH₂),C(Me)-(CH₂O), C(Me)(CHMeO), C(Me)-(CMe₂O), C(Me)-(CH₂S),C(Me)-(CH₂OCH₂), C(Me)(CHMeOCH₂), C(Me)-(CMe₂OCH₂), C(Me)-(CH₂S(O)₂CH₂),C(Me)-(CHMe-S(O)₂CH₂) or C(Me)-(CMe₂-S(O)₂CH₂), preferably B iscyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted byhalogen, C₁-C₄alkyl, hydroxy, cyano, C₁-C₄alkoxy or C₁-C₄alkylthio.

The process for the preparation of a compound of the formula V or, whereappropriate, a tautomer thereof, in each case in free form or in saltform, comprises, for example, to prepare a compound of formula V or,where appropriate, a tautomer and/or salt thereof, by reacting acompound of the formula

In which R₁, R₂, n have the meanings given in the formula I with acompound of formula

HN(R₃)-(A)_(q)-(X)_(p)—Y—B   (III),

in which R₃, p, q, A, X, Y and B have the meanings given for the formulaI, or, where appropriate, with a tautomer and/or salt thereof.

What has been said above for tautomers and/or salts of compounds Iapplies analogously to starting materials mentioned hereinabove andhereinbelow with regard to the tautomers and/or salts thereof.

The reactions described hereinabove and hereinbelow are carried out in amanner known per se, for example in the absence or, normally, in thepresence of a suitable solvent or diluent or of a mixture of these, theprocess being carried out, as required, with cooling, at roomtemperature or with heating, for example in a temperature range of fromapproximately −80° C. to the boiling point of the reaction mixture,preferably from approximately −20° C. to approximately +150° C., and, ifrequired, in a sealed vessel, under reduced, normal or elevatedpressure, in an inert gas atmosphere and/or under anhydrous conditions.Especially advantageous reaction conditions can be seen from theexamples.

Unless otherwise specified, the starting materials mentioned hereinaboveand hereinbelow, which are used for the preparation of the compounds Ior, where appropriate, the tautomers thereof, in each case in free formor in salt form, are known or can be prepared by methods known per se,for example in accordance with the information given below.

Variant a)

The reactants can be reacted with each other as such, i. e. withoutaddition of a solvent or diluent, for example in the melt. In mostcases, however, it is advantageous to add an inert solvent or diluent ora mixture of these. Examples of such solvents or diluents which may bementioned are: aromatic, aliphatic and alicyclic hydrocarbons andhalohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin,chlorobenzene, dichlorobenzene, bromo-benzene, petroleum ether, hexane,cyclohexane, dichloromethane, trichloromethane, tetra-chloromethane,dichloroethane, trichloroethene or tetrachloroethene; esters such asethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropylether, dibutyl ether, tert-butyl methyl ether, ethyleneglycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such asacetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, suchas methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol orglycerol; amides such as N,N-di-methylformamide, N,N-diethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphorictriamide; nitriles, such as acetonitrile or propionitrile; andsulfoxides, such as dimethyl sulfoxide.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between room temperature and approximately +80° C.

Variant b)

Examples of suitable leaving groups X₁ in the compounds IV are hydroxy,C₁-C₈alkoxy, halo-C₁-C₈alkoxy, C₁-C₈alkanoyloxy, mercapto,C₁-C₈alkylthio, halo-C₁-C₈alkylthio, C₁-C₈alkylsulfonloxy,halo-C₁-C₈alkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy andhalogen, such as chlorine. Preferred are hydroxy, C₁-C₈alkoxy andchlorine.

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. Examples ofsuitable solvents or diluents are of the type described under varianta).

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −20° C. to approximately +100° C., in many cases in therange between room temperature and the reflux temperature of thereaction mixture.

Variant c)

Examples of suitable leaving groups X₂ in the compounds VI are hydroxy,C₁-C₈alkoxy, halo-C₁-C₈alkoxy, C₁-C₈alkanoyloxy, mercapto,C₁-C₈alkylthio, halo-C₁-C₈alkylthio, C₁-C₈alkylsulfonyloxy,halo-C₁-C₈alkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy andhalogen, such as chlorine. Preferred are hydroxy and chlorine.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases for facilitating the detachment of HX₂ are alkali metalor alkaline earth metal hydroxides, alkali metal or alkaline earth metalhydrides, alkali metal or alkaline earth metal amides, alkali metal oralkaline earth metal alkoxides, alkali metal or alkaline earth metalacetates, alkali metal or alkaline earth metal carbonates, alkali metalor alkaline earth metal dialkylamides or alkali metal or alkaline earthmetal alkylsilylamides, alkylamines, alkylenediamines, free orN-alkylated saturated or unsaturated cycloalkylamines, basicheterocycles, ammonium hydroxides and carbocyclic amines. Examples whichmay be mentioned are sodium hydroxide, sodium hydride, sodium amide,sodium methoxide, sodium acetate, sodium carbonate, potassiumtert-butoxide, potassium hydroxide, potassium carbonate, potassiumhydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide,calcium hydride, triethylamine, diisopropylethylamine,triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine,N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine,quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. Examples ofsuitable solvents or diluents are of the type described under varianta). If the reaction is carried out in the presence of a base, baseswhich are employed in excess, such as triethylamine, pyridine,N-methylmorpholine or N,N-diethylaniline, may also act as solvents ordiluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between room temperature and approximately +80° C.

A compound I can be converted in a manner known per se into anothercompound I by replacing one or more substituents of the startingcompound I in the customary manner by (an)other substituent(s) accordingto the invention.

For example,

in compounds I, in which R₂ is hydrogen, this hydrogen R₂ can bereplaced by a substituent R₂, which is different from hydrogen; or

in compounds I, in which R₃ is hydrogen, this hydrogen R₃ can bereplaced by a substituent R₃, which is different from hydrogen.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds I can be prepared in a manner known per se. Thus, forexample, acid addition salts of compounds I are obtained by treatmentwith a suitable acid or a suitable ion exchanger reagent and salts withbases are obtained by treatment with a suitable base or with a suitableion exchanger reagent.

Salts of compounds I can be converted in the customary manner into thefree compounds I, acid addition salts, for example, by treatment with asuitable basic compound or with a suitable ion exchanger reagent andsalts with bases, for example, by treatment with a suitable acid or witha suitable ion exchanger reagent.

Salts of compounds I can be converted in a manner known per se intoother salts of compounds I, acid addition salts, for example, into otheracid addition salts, for example by treatment of a salt of inorganicacid such as hydrochloride with a suitable metal salt such as a sodium,barium or silver salt, of an acid, for example with silver acetate, in asuitable solvent in which an inorganic salt which forms, for examplesilver chloride, is insoluble and thus precipitates from the reactionmixture.

Depending on the procedure or the reaction conditions, the compounds I,which have salt-forming properties can be obtained in free form or inthe form of salts.

The compounds I and, where appropriate, the tautomers thereof, in eachcase in free form or in salt form, can be present in the form of-one ofthe isomers which are possible or as a mixture of these, for example inthe form of pure isomers, such as antipodes and/or diastereomers, or asisomer mixtures, such as enantiomer mixtures, for example racemates,diastereomer mixtures or racemate mixtures, depending on the number,absolute and relative configuration of asymmetric carbon atoms whichoccur in the molecule and/or depending on the configuration ofnon-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds I, in free formor in salt form, which can be obtained depending on which startingmaterials and procedures have been chosen can be separated in a knownmanner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl celulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds according to the invention and, where appropriate, thetautomers thereof, in each case in free form or in salt form, can, ifappropriate, also be obtained in the form of hydrates and/or includeother solvents, for example those which may have been used for thecrystallization of compounds which are present in solid form.

The compounds according to the invention are preventively and/orcuratively valuable active ingredients in the field of pest control,even at low rates of application, which have a very favorable biocidalspectrum and are well tolerated by warm-blooded species, fish andplants. The active ingredients according to the invention act againstall or individual developmental stages of normally sensitive, but alsoresistant, animal pests, such as insects or representatives of the orderAcarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,Olygonychus pratensis, Ornithodoros spp., Panonychus spp.,Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp.,Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp.and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp.,Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrusspp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinusspp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. andTrogoderma spp.;

from the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphoraerythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebraspp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilusspp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoliaspp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletispomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.;

from the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodniusspp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;

from the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplasterspp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccushesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotusspp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphisspp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae andUnaspis citri;

from the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpiniapolytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprionspp., Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

Reticulitermes spp.;

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,Carposina nipponensis, Chilo spp., Choristoneura spp., Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaspp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp.,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis,Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella,Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,Pectinophora gossypiela, Phthorimaea operculella, Pieris rapae, Pierisspp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp.,Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp.,Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Periplaneta spp. and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example, Frankliniella spp.,Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thripspalmi and Thrips tabaci; and

from the order Thysanura, for example,

Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca(preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

The term “crops” is to be understood as including also crops that havebeen rendered tolerant to herbicides like bromoxynil or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, forexample primisulfuron, prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady®, Herculex I® and LibertyLink®.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). Truncated toxins, forexample a truncated CryIA(b), are known. In the case of modified toxins,one or more amino acids of the naturally occurring toxin are replaced.In such amino acid replacements, preferably non-naturally presentprotease recognition sequences are inserted into the toxin, such as, forexample, in the case of CryIIIA055, a cathepsin-D-recognition sequenceis inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Boligard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIA toxin);Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin. Bt176 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIIIA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NU00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compounds according to the invention are theprotection of stored goods and storerooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

In the hygiene sector, the compounds according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohifahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compounds according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymeric substances, which comprise—at least—one ofthe active ingredients according to the invention and which are to beselected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable particulate adsorptive carriersfor granules are porous types, such as pumice, brick grit, sepiolite orbentonite, and suitable non-sorptive carrier materials are calcite orsand. In addition, a large number of granulated materials of inorganicor organic nature can be used, in particular dolomite or comminutedplant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having1 to approximately 10 carbon atoms in the alkyl chain and approximately20 to approximately 250 ethylene glycol ether groups and approximately10 to approximately 100 propylene glycol ether groups. Normally, theabovementioned compounds contain 1 to approximately 5 ethylene glycolunits per propylene glycol unit. Examples which may be mentioned arenonylphenoxypolyethoxyethanol, castor oil polyglycol ether,polypropylene glycol/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a pnonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%,of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at leastone solid or liquid adjuvant, it being possible as a rule for 0 to 25%,especially 0.1 to 20%, of the composition to be surfactants(% in eachcase meaning percent by weight). Whereas concentrated compositions tendto be preferred for commercial goods, the end consumer as a rule usesdilute compositions which have substantially lower concentrations ofactive ingredient. Preferred compositions are composed in particular asfollows (%=percent by weight):

Emulsifiable concentrates: active ingredient:   1 to 95%, preferably 5to 20% surfactant:   1 to 30%, preferably 10 to 20% solvent:   5 to 98%,preferably 70 to 85% Dusts: active ingredient:  0.1 to 10%, preferably0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspensionconcentrates: active ingredient:   5 to 75%, preferably 10 to 50% water:  94 to 24%, preferably 88 to 30% surfactant:   1 to 40%, preferably 2to 30% Wettable powders: active ingredient:  0.5 to 90%, preferably 1 to80% surfactant:  0.5 to 20%, preferably 1 to 15% solid carrier:   5 to99%, preferably 15 to 98% Granulates: active ingredient:  0.5 to 30%,preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions can also comprise further solid or liquid auxiliaries,such as stabilizers, for example unepoxidized or epoxidized vegetableoils (for example epoxidized coconut oil, rapeseed oil or soya oil),antifoams, for example silicone oil, preservatives, viscosityregulators, binders and/or tackifiers, fertilizers or other activeingredients for achieving specific effects, for example bactericides,fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers or kernels, or nursery plants, against pests of theabovementioned type. The propagation material can be treated with thecompositions prior to planting, for example seed can be treated prior tosowing. Alternatively, the compositions can be applied to seed kernels(coating), either by soaking the kernels in a liquid composition or byapplying a layer of a solid composition. It is also possible to applythe compositions when the propagation material is planted to the site ofapplication, for example into the seed furrow during drilling. Thesetreatment methods for plant propagation material and the plantpropagation material thus treated are further subjects of the invention.

PREPARATION EXAMPLES Example P1 Preparation of2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid [2-(bicyclopropyl-1-ylcarbamoyl)-4-cyano-6-methyl-phenyl]-amide(A.1.1)

To a solution of2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-8-methyl-4-oxo-4H-benzo[d][1,3]oxazine-6-carbonitrile(1.2 g, 2,8 mmol) (prepared according to WO 04/067528) intetrahydrofuran (40 ml), is added bicyclopropyl-1-ylamine hydrochloride(0.6 g, 4.2 mmol) and 1.2 ml (8.4 mmol) triethylamine, and the solutionis heated at a temperature of 60° C. for 8 h. The solution is cooleddown to ambient temperature and the solvent is evaporated. Then themixture is triturated in 100 ml water and the crystals are washed withwater and ether to afford 0.85 g of the title compound. The motherliquor is evaporated and a second crop of crystals is obtained bycrystallisation in diisopropylether to afford 0.46 g of the titlecompound (F: 270-272° C.).

Example P2 Preparation of2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid [2-(bicyclopropyl-1-ylcarbamoyl)-4-cyano-6-methyl-phenyl]-amide(A.1.1)

To a solution of 3.29 g (5.23 mmol)2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid [2-(bicyclopropyl-1 -ylcarbamoyl)-4-iodo-6-methyl-phenyl]-amide in50 ml tetrahydrofuran is added 1.19 g (6.25 mmol) Cul, 0.30 gtetrakis(triphenylphosphine) palladium and 2.78 g (31.0 mmol) CuCN. Themixture is heated 1 h at 80° C. and turns dark green. After coolingdown, the mixture is filtered on Hyflo and evaporated. The residue isdissolved in 15 ml DMF and poured into 100 ml water containing 5 gNaHCO₃. After 30 min stirring, the crystals are filtered, washed withwater and a mixture of hexane/acetone (1:3) to afford 2.8 g of the titlecompound.

Preparation of2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylicacid [2-(bicyclopropyl-1-ylcarbamoyl)-4-iodo-6-methyl-phenyl]-amide

2.08 g (3.91 mmol)(2-[2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazol-3-yl]-8-hydroxy-6-iodo-benzo[d][1,3]oxazin-4-one(prepared according to WO 04/067528), 0.6 g (4.50 mmol)bicyclopropyl-1-ylamine hydrochloride and 0.63 ml (4.50 mmol)triethylamine in 20 ml THF are heated 20 h at reflux. After coolingdown, the precipitate is filtered and the mother liquor is evaporated.The residue is dissolved in 5 ml DMF and poured into 40 ml water. Thecrystals formed are filtered and purified by flash-chromatography(dichloromethane 40, diethylether 1) to afford 1.85 g title compound.¹H-NMR (CDCl₃, 400 MHz. ppm): 0.11 (q, 2H), 0.45 (q, 2H), 0.62 (s, 4H),1.4 (m, 1H), 2.10 (s, 3H), 6.50 (s, 1H), 7.40 (m, 2H), 7.51 (s, 1H),7.77 (s, 1H), 7.85 (dd, 1H), 8.49 (m, 1H), 10.45 (s, 1H).

Preparation of 2-Amino-N-bicyclopropyl-1-yl-5-cyano-3-methyl-benzamide

600 mg (1.98 mmol) 6-iodo-8-methyl-1H-benzo[d][1,3]oxa zine-2,4-dione(prepared according to known procedures, see G. M. Coppola, Synthesis,1980, 505), 212 mg (2.37 mmol) CuCN, 377 mg (1.98 mmol) Cul and 114 mgtetrakis(triphenylphosphine) palladium in 60 ml THF are heated 5 h atreflux. After cooling down, the mixture is filtered on Hyflo. Theorganic phase is washed with water and evaporated. The residue iscrystallized from a mixture of dichloromethane, ethyl acetate and hexaneto afford 245 mg8-methyl-2,4-dioxo-1,4-dihydro-2H-benzo[d][1,3]oxazine-6-carbonitrile,which is directly used in the next step.

236 mg (1.16 mmol)8-methyl-2,4-dioxo-1,4-dihydro-2H-benzo[d][1,3]oxazine-6-carbonitrile,234 mg (1.75 mmol) bicyclopropyl-1-ylamine hydrochloride and 177 mg(1.75 mmol) triethylamine in 25 ml THF are heated 4 h at reflux. Themixture is cooled down and evaporated. The residue is dissolved in ethylacetate and extracted with water. After purification on a short path ofsilicagel, 63 mg of the title compound are isolated as yellow crystals.F: 171-172° C.

Preparation of bicyclopropyl-1-ylamine

93.2 ml (328 mmol) Ti(OiPr)₄ is added to a solution of 20 g (298 mmol)cyclopropane carbonitrile in 300 ml ether. Then the solution is cooleddown to −78° C. and 199 ml (596 mmol) ethylmagnesium bromide solution (3M in ether) are slowly added. After 10 min at −78° C., the slurry isallowed to warm up to ambient temperature and stirred for 1 hour. Then84.6 g (595 mmol) BF₃.OEt₂ is added and the mixture is stirred atambient temperature for 18 hours. To this mixture, 600 ml NaOH 2N isslowly added at a temperature of 0° C. The organic phase is separatedand extracted with 600 ml HCl 2N. The water phase is evaporated and theresidue is triturated in ether to afford 30.9 g of the title compound asan hydrochloride salt.

The examples which follow are intended to illustrate the invention andshow preferred compounds of formula I. Me means the methyl group. Etmeans the ethyl group. If no definition for substituent X is given, thenp is 0, if X is a substituent, then p is 1. If no definition forsubstituent A is given, then q is 0, if A is a substituent, then q is 1.The group C(CH₂CH₂) for the substituent Y means cyclopropyl with twofree valences:

TABLE A Compounds of formula Ia: (Ia)

Comp. No. R₉₁ R₉₃ A X Y B A.1.1 Me CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.2Cl CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.3 Br CF₃ — — C(CH₂CH₂)cyclo-propyl A.1.4 Me Cl — — C(CH₂CH₂) cyclo-propyl A.1.5 Cl Cl — —C(CH₂CH₂) cyclo-propyl A.1.6 Br Cl — — C(CH₂CH₂) cyclo-propyl A.1.7 MeBr — — C(CH₂CH₂) cyclo-propyl A.1.8 Cl Br — — C(CH₂CH₂) cyclo-propylA.1.9 Br Br — — C(CH₂CH₂) cyclo-propyl A.1.10 Me OCHF₂ — — C(CH₂CH₂)cyclo-propyl A.1.11 Cl OCHF₂ — — C(CH₂CH₂) cyclo-propyl A.1.12 Br OCHF₂— — C(CH₂CH₂) cyclo-propyl A.1.13 Me OCH₂CF₃ — — C(CH₂CH₂) cyclo-propylA.1.14 Cl OCH₂CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.15 Br OCH₂CF₃ — —C(CH₂CH₂) cyclo-propyl A.1.16 Me CHF₂ — — C(CH₂CH₂) cyclo-propyl A.1.17Cl CHF₂ — — C(CH₂CH₂) cyclo-propyl A.1.18 Br CHF₂ — — C(CH₂CH₂)cyclo-propyl A.1.19 Me CH₂CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.20 ClCH₂CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.21 Br CH₂CF₃ — — C(CH₂CH₂)cyclo-propyl A.1.22 Me CF₃ — — CH(cyclo- cyclo-propyl propyl) A.1.23 MeCF₃ — — C(CH₂CH₂) cyclo-propyl A.1.24 Me CF₃ — — C(CH₂CHF) cyclo-propylA.1.25 Me CF₃ — — C(CH₂CF₂) cyclo-propyl A.1.26 Me CF₃ — — C(CH₂CHCl)cyclo-propyl A.1.27 Me CF₃ — — C(CH₂CFCl) cyclo-propyl A.1.28 Me CF₃ — —C(CH₂CCl₂) cyclo-propyl A.1.29 Me CF₃ — — C(CH₂CHBr) cyclo-propyl A.1.30Me CF₃ — — C(CH₂CBr₂) cyclo-propyl A.1.31 Me CF₃ C(CH₂CHMe) — C(CH₂CHMe)cyclo-propyl A.1.32 Me CF₃ — C(CH₂CMe₂) cyclo-propyl A.1.33 Me CF₃ —C(CH₂CHEt) cyclo-propyl A.1.34 Me CF₃ — C(CH₂CEt₂) cyclo-propyl A.1.35Me CF₃ — C(CH₂OCH₂) cyclo-propyl A.1.36 Me CF₃ — C(CH₂S(O)₂—CH₂cyclo-propyl A.1.37 Me CF₃ C(CH₂CH₂) O C(CH₂CH₂) cyclo-propyl A.1.38 MeCF₃ CH₂ CH₂ C(CH₂CH₂) cyclo-propyl A.1.39 Me CF₃ CH₂ O CH-(cyclo-cyclo-propyl propyl) A.1.40 Me CF₃ CH₂ O CH(CH₂S—(O)₂Me) cyclo-propylA.1.41 Me CF₃ CH₂ O CH(CH₂O-Me) cyclo-propyl A.1.42 Me CF₃ CH₂ OC(CH₂CH₂) cyclo-propyl A.1.43 Me CF₃ CH₂ O C(CH₂CHF) cyclo-propyl A.1.44Me CF₃ CH₂ O C(CH₂CF₂) cyclo-propyl A.1.45 Me CF₃ CH₂ O C(CH₂CHCl)cyclo-propyl A.1.46 Me CF₃ CH₂ O C(CH₂CFCl) cyclo-propyl A.1.47 Me CF₃CH₂ O C(CH₂CCCl₂) cyclo-propyl A.1.48 Me CF₃ CH₂ O C(CH₂CHBr)cyclo-propyl A.1.49 Me CF₃ CH₂ O C(CH₂CBr₂) cyclo-propyl A.1.50 Me CF₃CH₂ O C(CH₂CHMe) cyclo-propyl A.1.51 Me CF₃ CH₂ O C(CH₂CMe₂)cyclo-propyl A.1.52 Me CF₃ CH₂ O C(CH₂CHEt) cyclo-propyl A.1.53 Me CF₃CH₂ O C(CH₂C-Et₂) cyclo-propyl A.1.54 Me CF₃ — — C(CH₂CH₂)1-fluoro-cyclo-propyl A.1.55 Me CF₃ — — C(CH₂CH₂) 1-chloro-cyclo-propylA.1.56 Me CF₃ — — C(CH₂CH₂) 1-bromo-cyclo- propyl A.1.57 Me CF₃ — —C(CH₂CH₂) 1-methyl--cyclo- propyl A.1.58 Me CF₃ — — C(CH₂CH₂)1-ethyl-cyclo-propyl A.1.59 Me CF₃ — — C(CH₂CH₂) 1-cyano-cyclo-propylA.1.60 Me CF₃ — — C(CH₂CH₂) 1-methyl--thiocyclo- propyl A.1.61 Me CF₃ —— C(CH₂CH₂) 1-methoxy-cyclo- propyl A.1.62 Me CF₃ — — C(CH₂CH₂)1-hydroxy-cyclo- propyl A.1.63 Me CF₃ — — C(CH₂CH₂) 1-trifluoro-methyl-cyclo-propyl A.1.64 Me CF₃ — — C(CH₂CH₂) 2-fluoro-cyolo-propyl A.1.65 MeCF₃ — — C(CH₂CH₂) 2,2-difluoro-cyclo- propyl A.1.66 Me CF₃ — — C(CH₂CH₂)2-chloro-cyclo-propyl A.1.67 Me CF₃ — — C(CH₂CH₂) 2,2-dichloro-cyclo-propyl A.1.68 Me CF₃ — — C(CH₂CH₂) 2-bromo-cyclo- propyl A.1.69 Me CF₃ —— C(CH₂CH₂) 2,2-dibromo-cyclo- propyl A.1.70 Me CF₃ — — C(CH₂CH₂)2-chloro-2-fluoro- cyclo-propyl A.1.71 Me CF₃ — — C(CH₂CH₂)2-methyl-cyclo- propyl A.1.72 Me CF₃ — — C(CH₂CH₂) 2,2-dimethyl-cyclo-propyl A.1.73 Me CF₃ — — C(CH₂CH₂) 2-ethyl-cyclo-propyl A.1.74 Me CF₃ —— C(CH₂CH₂) 2,2-diethyl-cyclo- propyl A.1.75 Me CF₃ — — C(CH₂CH₂)2-cyano-cyclo-propyl A.1.76 Me CF₃ — — C(CH₂CH₂) 2-methyl-thiocyclo-propyl A.1.77 Me CF₃ — — C(CH₂CH₂) 2-methoxy-cyclo- propyl A.1.78 Me CF₃— — C(CH₂CH₂) 2-hydroxy-cyclo- propyl A.1.79 Me CF₃ — — C(CH₂CH₂)2-trifluoro-methyl-- cyclo-propyl A.1.80 Me CF₃ — — C(CH₂CH₂)cyclo-butyl A.1.81 Me CF₃ — — C(CH₂CH₂) 2-fluoro-cyclo-butyl A.1.82 MeCF₃ — — C(CH₂CH₂) 2,2-difluoro-cyclo- butyl A.1.83 Me CF₃ — — C(CH₂CH₂)2-chloro-cyclo-butyl A.1.84 Me CF₃ — — C(CH₂CH₂) 2,2-dichloro-cyclo-butyl A.1.85 Me CF₃ — — C(CH₂CH₂) 2-bromo-cyclo-butyl A.1.86 Me CF₃ — —C(CH₂CH₂) 2,2-dibromo-cyclo- butyl A.1.87 Me CF₃ — — C(CH₂CH₂)2-chloro-2-fluoro- cyclo-butyl A.1.88 Me CF₃ — — C(CH₂CH₂)2-methyl-cyclo-butyl A.1.89 Me CF₃ — — C(CH₂CH₂) 2,2-dimethyl--cyclo-butyl A.1.90 Me CF₃ — — C(CH₂CH₂) 2-ethyl-cyclo-butyl A.1.91 Me CF₃ — —C(CH₂CH₂) 2,2-diethyl-cyclo- butyl A.1.92 Me CF₃ — — C(CH₂CH₂)2-cyano-cyclo-butyl A.1.93 Me CF₃ — — C(CH₂CH₂) 2-methyl-thiocyclo-butyl A.1.94 Me CF₃ — — C(CH₂CH₂) 2-methoxy-cyclo- butyl A.1.95 Me CF₃ —— C(CH₂CH₂) 2-hydroxy-cyclo- butyl A.1.96 Me CF₃ — — C(CH₂CH₂)2-trifluoro-methyl- cyclo-butyl A.1.97 Me CF₃ — — C(CH₂CH₂)3-methyl-cyclo-butyl A.1.98 Me CF₃ — — C(CH₂CH₂) 3,3-dimethyl--cyclo-butyl A.1.99 Me CF₃ — — C(CH₂CH₂) 3-chloro-cyclo-butyl A.1.100 Me CF₃ —— C(CH₂CH₂) 3,3-dichloro-cyclo- butyl A.1.101 Me CF₃ — — C(CH₂CH₂)CH(CH₂O) A.1.102 Me CF₃ — — C(CH₂CH₂) CH(CH-MeO) A.1.103 Me CF₃ — —C(CH₂CH₂) CH(C-Me₂O) A.1.104 Me CF₃ — — C(CH₂CH₂) CH(CH₂S) A.1.105 MeCF₃ — — C(CH₂CH₂) CH(CH₂OCH₂) A.1.106 Me CF₃ — — C(CH₂CH₂) CH(CHMeOCH₂)A.1.107 Me CF₃ — — C(CH₂CH₂) CH(CMe₂OCH₂) A.1.108 Me CF₃ — — C(CH₂CH₂)CH(CH₂—S(O)₂CH₂) A.1.109 Me CF₃ — — C(CH₂CH₂) CH(CHMeS(O)₂CH₂) A.1.110Me CF₃ — — C(CH₂CH₂) CH(CMe₂S(O)₂CH₂) A.1.111 Me CF₃ — — C(CH₂CH₂)C(Me)-(CH₂O) A.1.112 Me CF₃ — — C(CH₂CH₂) C(Me)-(CHMeO) A.1.113 Me CF₃ —— C(CH₂CH₂) C(Me)-(CMe₂O) A.1.114 Me CF₃ — — C(CH₂CH₂) C(Me)-(CH₂S)A.1.115 Me CF₃ — — C(CH₂CH₂) C(Me)-(CH₂OCH₂) A.1.116 Me CF₃ — —C(CH₂CH₂) C(Me)-(CHMeO—CH₂) A.1.117 Me CF₃ — — C(CH₂CH₂)C(Me)-(C-Me₂OCH₂) A.1.118 Me CF₃ — — C(CH₂CH₂) C(Me)- (CH₂S(O)₂CH₂)A.1.119 Me CF₃ — — C(CH₂CH₂) C(Me)-(CH- MeS(O)₂CH₂) A.1.120 Me CF₃ — —C(CH₂CH₂) CMe(C- Me₂S(O)₂CH₂) A.1.121 Me CF₃ — — C(CH₂CH₂)1-(COOEt)-cyclo- propyl A.1.122 Me SMe — — C(CH₂CH₂) cyclo-propylA.1.123 Cl SMe — — C(CH₂CH₂) cyclo-propyl A.1.124 Br SMe — — C(CH₂CH₂)cyclo-propyl A.1.125 Me SOMe — — C(CH₂CH₂) cyclo-propyl A.1.126 Cl SOMe— — C(CH₂CH₂) cyclo-propyl A.1.127 Br SOMe — — C(CH₂CH₂) cyclo-propylA.1.128 Me SO₂Me — — C(CH₂CH₂) cyclo-propyl A.1.129 Cl SO₂Me — —C(CH₂CH₂) cyclo-propyl A.1.130 Br SO₂Me — — C(CH₂CH₂) cyclo-propylA.1.131 Me OCF₂CFHCF₃ — — C(CH₂CH₂) cyclo-propyl A.1.132 Cl OCF₂CFHCF₃ —— C(CH₂CH₂) cyclo-propyl A.1.133 Br OCF₂CFHCF₃ — — C(CH₂CH₂)cyclo-propyl A.1.134 Me OCH₂CF₂CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.135 ClOCH₂CF₂CF₃ — — C(CH₂CH₂) cyclo-propyl A.1.136 Br OCH₂CF₂CF₃ — —C(CH₂CH₂) cyclo-propyl

TABLE B Compounds of formula Ib: (Ib)

Comp. No. R₉₁ R₉₃ R₉₄ A X Y B B.1.1 Me CF₃ Br — — C(CH₂CH₂) cyclo-propylB.1.2 Cl CF₃ Br — — C(CH₂CH₂) cyolo-propyl B.1.3 Br CF₃ Br — — C(CH₂CH₂)cyclo-propyl B.1.4 Me Cl Br — — C(CH₂CH₂) cyclo-propyl B.1.5 Cl Cl Br —— C(CH₂CH₂) cyclo-propyl B.1.6 Br Cl Br — — C(CH₂CH₂) cyclo-propyl B.1.7Me Br Br — — C(CH₂CH₂) cyclo-propyl B.1.8 Cl Br Br — — C(CH₂CH₂)cyclo-propyl B.1.9 Br Br Br — — C(CH₂CH₂) cyclo-propyl B.1.10 Me CF₃ Cl— — C(CH₂CH₂) cyclo-propyl B.1.11 Cl CF₃ Cl — — C(CH₂CH₂) cyclo-propylB.1.12 Br CF₃ Cl — — C(CH₂CH₂) cyclo-propyl B.1.13 Me Cl Cl — —C(CH₂CH₂) cyclo-propyl B.1.14 Cl Cl Cl — — C(CH₂CH₂) cyclo-propyl B.1.15Br Cl Cl — — C(CH₂CH₂) cyclo-propyl B.1.16 Me Br Cl — — C(CH₂CH₂)cyclo-propyl B.1.17 Cl Br Cl — — C(CH₂CH₂) cyclo-propyl B.1.18 Br Br Cl— — C(CH₂CH₂) cyclo-propyl B.1.19 Me CF₃ Me — — C(CH₂CH₂) cyclo-propylB.1.20 Cl CF₃ Me — — C(CH₂CH₂) cyclo-propyl B.1.21 Br CF₃ Me — —C(CH₂CH₂) cyclo-propyl B.1.22 Me Cl Me — — C(CH₂CH₂) cyclo-propyl B.1.23Cl Cl Me — — C(CH₂CH₂) cyclo-propyl B.1.24 Br Cl Me — — C(CH₂CH₂)cyclo-propyl B.1.25 Me Br Me — — C(CH₂CH₂) cyclo-propyl B.1.26 Cl Br Me— — C(CH₂CH₂) cyclo-propyl B.1.27 Br Br Me — — C(CH₂CH₂) cyclo-propylB.1.28 Me OCH₂CF₃ Br — — C(CH₂CH₂) cyclo-propyl B.1.29 Cl OCH₂CF₃ Br — —C(CH₂CH₂) cyclo-propyl B.1.30 Br OCH₂CF₃ Br — — C(CH₂CH₂) cyclo-propylB.1.31 Me OCH₂CF₃ Cl — — C(CH₂CH₂) cyclo-propyl B.1.32 Cl OCH₂CF₃ Cl — —C(CH₂CH₂) cyclo-propyl B.1.33 Br OCH₂CF₃ Cl — — C(CH₂CH₂) cyclo-propylB.1.34 Me OCH₂CF₃ Me — — C(CH₂CH₂) cyclo-propyl B.1.35 Cl OCH₂CF₃ Me — —C(CH₂CH₂) cyclo-propyl B.1.36 Br OCH₂CF₃ Me — — C(CH₂CH₂) cyclo-propyl

TABLE C Physical data of the compounds of table A and B: Compound m.p.No. [° C.] A.1.1 270-272 A.1.13 175-178 A.1.4 249-255 A.1.7 254-260B.1.28 169-174 A.1.122 243-244 A.1.131 170-172 A.1.134 200-205 A.1.16250-251 A.1.72 158-160 A.1.57 247-249

TABLE D Compounds of formula Va: (Va)

Comp. m.p. No. R₉₁ Y B [° C.] D1 Me C(CH₂CH₂) cyclo-propyl 171-172 D2 MeCH(cyclo-propyl) cyclo-propyl D3 Me C(CH₂CHF) cyclo-propyl D4 MeC(CH₂CF₂) cyclo-propyl D4 Me C(CH₂CHCl) cyclo-propyl D6 Me C(CH₂CFCl)cyclo-propyl D7 Me C(CH₂CCl₂) cyclo-propyl D8 Me C(CH₂CHBr) cyclo-propylD9 Me C(CH₂CBr₂) cyclo-propyl D11 Me C(CH₂CMe₂) cyclo-propyl D12 MeC(CH₂CHEt) cyclo-propyl D13 Me C(CH₂CEt₂) cyclo-propyl D14 Me C(CH₂OCH₂)cyclo-propyl D15 Me C(CH₂S(O)₂—CH₂ cyclo-propyl D16 Me C(CH₂CH₂)1-fluoro-cyclo-propyl D17 Me C(CH₂CH₂) 1-chloro-cyclo-propyl D18 MeC(CH₂CH₂) 1-bromo-cyclo-propyl D19 Me C(CH₂CH₂) 1-methyl--cyclo-propylD20 Me C(CH₂CH₂) 1-ethyl-cyclo-propyl D21 Me C(CH₂CH₂)1-cyano-cyclo-propyl D22 Me C(CH₂CH₂) 1-methyl--thiocyclo-propyl D23 MeC(CH₂CH₂) 1-methoxy-cyclo-propyl D24 Me C(CH₂CH₂) 1-hydroxy-cyclo-propylD25 Me C(CH₂CH₂) 1-trifluoro-methyl-cyclo-propyl D26 Me C(CH₂CH₂)2-fluoro-cyclo-propyl D27 Me C(CH₂CH₂) 2,2-difluoro-cyclo-propyl D28 MeC(CH₂CH₂) 2-chloro-cyclo-propyl D29 Me C(CH₂CH₂)2,2-dichloro-cyclo-propyl D30 Me C(CH₂CH₂) 2-bromo-cyclo-propyl D31 MeC(CH₂CH₂) 2,2-dibromo-cyclo-propyl D32 Me C(CH₂CH₂)2-chloro-2-fluoro-cyclo-propyl D33 Me C(CH₂CH₂) 2-methyl-cyclo-propylD34 Me C(CH₂CH₂) 2,2-dimethyl-cyclo-propyl D35 Me C(CH₂CH₂)2-ethyl-cyclo-propyl D36 Me C(CH₂CH₂) 2,2-diethyl-cyclo-propyl D37 MeC(CH₂CH₂) 2-cyano-cyclo-propyl D38 Me C(CH₂CH₂)2-methyl-thiocyclo-propyl D39 Me C(CH₂CH₂) 2-methoxy-cyclo-propyl D40 MeC(CH₂CH₂) 2-hydroxy-cyclo-propyl D41 Me C(CH₂CH₂)2-trifluoro-methyl-cyclo-propyl D42 Me C(CH₂CH₂) cyclo-butyl D43 MeC(CH₂CH₂) 2-fluoro-cyclo-butyl D44 Me C(CH₂CH₂) 2,2-difluoro-cyclo-butylD45 Me C(CH₂CH₂) 2-chloro-cyclo-butyl D46 Me C(CH₂CH₂)2,2-dichloro-cyclo-butyl D47 Me C(CH₂CH₂) 2-bromo-cyclo-butyl D48 MeC(CH₂CH₂) 2,2-dibromo-cyclo-butyl D49 Me C(CH₂CH₂)2-chloro-2-fluoro-cyclo-butyl D50 Me C(CH₂CH₂) 2-methyl-cyclo-butyl D51Me C(CH₂CH₂) 2,2-dimethyl--cyclo-butyl D52 Me C(CH₂CH₂)2-ethyl-cyclo-butyl D53 Me C(CH₂CH₂) 2,2-diethyl-cyclo-butyl D54 MeC(CH₂CH₂) 2-cyano-cyclo-butyl D55 Me C(CH₂CH₂) 2-methyl-thiocyclo-butylD56 Me C(CH₂CH₂) 2-methoxy-cyclo-butyl D57 Me C(CH₂CH₂)2-hydroxy-cyclo-butyl D58 Me C(CH₂CH₂) 2-trifluoro-methyl-cyclo-butylD59 Me C(CH₂CH₂) 3-methyl-cyclo-butyl D60 Me C(CH₂CH₂)3,3-dimethyl--cyclo-butyl D61 Me C(CH₂CH₂) 3-chloro-cyclo-butyl D62 MeC(CH₂CH₂) 3,3-dichloro-cyclo-butyl D63 Me C(CH₂CH₂) CH(CH₂O) D64 MeC(CH₂CH₂) CH(CH-MeO) D65 Me C(CH₂CH₂) CH(C-Me₂O) D66 Me C(CH₂CH₂)CH(CH₂S) D67 Me C(CH₂CH₂) CH(CH₂OCH₂) D68 Me C(CH₂CH₂) CH(CHMeOCH₂) D69Me C(CH₂CH₂) CH(CMe₂OCH₂) D70 Me C(CH₂CH₂) CH(CH₂—S(O)₂CH₂) D71 MeC(CH₂CH₂) CH(CHMeS(O)₂CH₂) D72 Me C(CH₂CH₂) CH(CMe₂S(O)₂CH₂) D73 MeC(CH₂CH₂) C(Me)-(CH₂O) D74 Me C(CH₂CH₂) C(Me)-(CHMeO) D75 Me C(CH₂CH₂)C(Me)-(CMe₂O) D76 Me C(CH₂CH₂) C(Me)-(CH₂S) D77 Me C(CH₂CH₂)C(Me)-(CH₂OCH₂) D78 Me C(CH₂CH₂) C(Me)-(CHMeO-CH₂) D79 Me C(CH₂CH₂)C(Me)-(C-Me₂OCH₂) D80 Me C(CH₂CH₂) C(Me)-(CH₂S(O)₂CH₂) D81 Me C(CH₂CH₂)C(Me)-(CH-MeS(O)₂CH₂) D82 Me C(CH₂CH₂) CMe(C-Me₂S(O)₂CH₂) D83 MeC(CH₂CH₂) 1-(COOEt)-cyclo-propyl D84 Cl C(CH₂CH₂) cyclo-propyl D85 BrC(CH₂CH₂) cyclo-propyl D86 Cl C(CH₂CH₂) 1-methyl-cyclo-propyl D87 BrC(CH₂CH₂) 1-methyl-cyclo-propyl D88 Cl C(CH₂CH₂)2,2-dimethyl-cyclo-propyl D89 Br C(CH₂CH₂) 2,2-dimethyl-cyclo-propyl

Formulation examples (%=percent by weight)

EXAMPLE F1 Emulsion concentrates a) b) c) Active ingredient 25% 40% 50%Calcium dodecylbenzenesulfonate  5%  8%  6% Castor oil polyethyleneglycol ether (36 mol of EO)  5% — — Tributylphenoxypolyethylene glycolether — 12%  4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture65% 25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

EXAMPLE F2 Solutions a) b) c) d) Active ingredient 80% 10% 5% 95%Ethylene glycol monomethyl ether 20% — — — Polyethylene glycol MW 400 —70% — — N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1% 5% Petroleum ether (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

EXAMPLE F3 Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin94%  — 79% 54% Highly disperse silica 1% — 13%  7% Attapulgite — 90% —18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

EXAMPLE F4 Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1%5% Talc 97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

EXAMPLE F5 Wettable powders a) b) c) Active ingredient 25%  50% 75%Sodium lignosulfonate 5%  5% — Sodium lauryl sulfate 3% —  5% Sodiumdiisobutylnaphthalenesulfonate —  6% 10% Octylphenoxypolyethylene glycol—  2% — ether (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

EXAMPLE F6 Extruder granules Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose  1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

EXAMPLE F7 Coated granules Active ingredient 3% Polyethylene glycol (MW200) 3% Kaolin 94% 

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

EXAMPLE F8 Suspension concentrate Active ingredient 40% Ethylene glycol10% Nonylphenoxypolyethylene glycol ether (15 mol of EO)  6% Sodiumlignosulfonate 10% Carboxymethylcellulose  1% 37% aqueous formaldehydesolution 0.2%  Silicone oil (75% aqueous emulsion) 0.8%  Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

The activity of the compounds according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally or acaricidally active ingredients. Suitableadditions to active ingredients here are, for example, representativesof the following classes of active ingredients: organophosphoruscompounds, nitrophenol derivatives, thioureas, juvenile hormones,formamidines, benzophenone derivatives, ureas, pyrrole derivatives,carbamates, pyrethroids, chlorinated hydrocarbons, acylureas,pyridylmethyleneamino derivatives, macrolides, neonicotinoids andBacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds specificallydescribed in tables A and B of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos(920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin(99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben(alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX,camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX,carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50'439 (developmentcode) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulphide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel(alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternativename) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate(1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT(219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O(1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternativename)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX,dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)(653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton(269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX,dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX,dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPACname) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton(278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternativename) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX,eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1 157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, parathion (615)+TX, permethrin(626)+TX, petroleum oils (alternative name) (628)+TX, phenkapton(1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX,phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX, phoxim(642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes (traditionalname) (1347)+TX, polynactins (alternative name) (653)+TX, proclonol(1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX,propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX,prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX,pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion (701)+TX,pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos (711)+TX,quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, RA-17(development code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX,sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX,SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX,spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX, sulfiram(alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX,sulfur (754)+TX, SZI-121 (development code) (757)+TX, tau-fluvalinate(398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (alternativename)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX, tetranactin(alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox (alternativename)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon(801)+TX, thioquinox (1436)+TX, thuringiensin (alternative name)[CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

a bactericide selected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyidithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanli(alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E+TX,Z)-tetradeca-4+TX, 10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E+TX,9Z)-dodeca-7+TX, 9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z+TX,11E)-tetradeca-9+TX, 11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z+TX,12E)-tetradeca-9+TX, 12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, mediure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2+TX, 13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3 +TX, 13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)-ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of 1+TX,1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1+TX, 1-dichloro-2+TX, 2-bis(4-ethylphenyl)ethane (IUPAC name)(1056)+TX, 1+TX, 2-dichloropropane (IUPAC/Chemical Abstracts name)(1062)+TX, 1+TX, 2-dichloropropane with 1+TX, 3-dichloropropene (IUPACname) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name)(916)+TX, 2+TX, 2+TX, 2-trichloro-1-(3 +TX, 4-dichlorophenyl)ethylacetate (IUPAC name) (1451)+TX, 2+TX, 2-dichlorovinyl2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1+TX,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstractsname) (1109)+TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/ChemicalAbstracts name) (935)+TX, 2-(4+TX, 5-dimethyl-1+TX,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name)(1084)+TX, 2-(4-chloro-3+TX, 5-xylyloxy)ethanol (IUPAC name) (986)+TX,2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX, 2-imidazolidone(IUPAC name) (1225)+TX, 2-isovalerylindan-1+TX, 3-dione (IUPAC name)(1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name)(1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433)+TX,3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3+TX, 5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5+TX, 5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate(IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid(4)+TX, acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX,acrinathrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb(15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX,allethrin (17)+TX, allosamidin (alternative name) [CCN]+TX, allyxycarb(866)+TX, alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name)[CCN]+TX, aluminium phosphide (640)+TX, amidithion (870)+TX,amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX, amitonhydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX,athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compoundcode)+TX, azadirachtin (alternative name) (41)+TX, azamethiphos (42)+TX,azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX,Bacillus thuringiensis delta endotoxins (alternative name) (52)+TX,barium hexafluorosilicate (alternative name) [CCN]+TX, bariumpolysulfide (IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX,Bayer 22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethyinon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name)[CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenilehormone III (alternative name) [CCN]+TX, kelevan (1249)+TX, kinoprene(484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX,lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos(1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenylmethylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name)(640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX,mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan(1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX,metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (alternativename) (519)+TX, metam-sodium (519)+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC/ChemicalAbstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX,methocrotophos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX,methoquin-butyl (1276)+TX, methothrin (alternative name) (533)+TX,methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, methylchloroform (alternativename) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin [CCN]+TX,metoicarb (550)+TX, metoxadiazone (1288)+TX, mevinphos (556)+TX,mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1+TX, 2-dibromo-3-chloropropane(IUPAC/Chemical Abstracts name) (1045)+TX, 1+TX, 2-dichloropropane(IUPAC/Chemical Abstracts name) (1062)+TX, 1+TX, 2-dichloropropane with1+TX, 3-dichloropropene (IUPAC name) (1063)+TX, 1+TX, 3-dichloropropene(233)+TX, 3+TX, 4-dichlorotetrahydrothiophene 1+TX, 1-dioxide(IUPAC/Chemical Abstracts name) (1065)+TX,3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX,5-methyl-6-thioxo-1+TX, 3+TX, 5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1+TX, 3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)-ethyl piperonylate (IUPAC name) (934)+TX, 5-(1+TX,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

and a wound protectant selected from the group of substances consistingof mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

the compound of Formula A-1

the formula A-2

the formula A-3

the formula A-4

the formula A-5

the formula A-6

the formula A-7

the formula A-8

the formula A-9

the formula A-10

the formula A-11

the formula A-12

the formula A-13

the formula A-14

the formula A-15

the formula A-16

the formula A-17

the formula A-18

the formula A-19

the formula A-20

the formula A-21

the formula A-22

the formula A-23

the formula A-24

the formula A-25

the formula A-26

and Azaconazole (60207-31-0]+TX, Bitertanol [70585-36-3]+TX,Bromuconazole [116255-48-2]+TX, Cyproconazole [94361-06-5]+TX,Difenoconazole [119446-68-3]+TX, Diniconazole [83657-24-3]+TX,Epoxiconazole [106325-08-0]+TX, Fenbuconazole [114369-43-6]+TX,Fluquinconazole [136426-54-5]+TX, Flusilazole [85509-19-9]+TX,Flutriafol [76674-21-0]+TX, Hexaconazole [79983-71-4]+TX, Imazalil[35554-44-0]+TX, Imibenconazole [86598-92-7]+TX, Ipconazole[125225-28-7]+TX, Metconazole [125116-23-6]+TX, Myclobutanil[88671-89-0]+TX, Pefurazoate [101903-30-4]+TX, Penconazole[66246-88-6]+TX, Prothioconazole [178928-70-6]+TX, Pyrifenox[88283-41-4]+TX, Prochloraz [67747-09-5]+TX, Propiconazole[60207-90-1]+TX, Simeconazole [149508-90-7]+TX, Tebuconazole[107534-96-3]+TX, Tetraconazole [112281-77-3]+TX, Triadimefon[43121-43-3]+TX, Triadimenol [55219-65-3]+TX, Triflumizole[99387-89-0]+TX, Triticonazole [131983-72-7]+TX, Ancymidol[12771-68-5]+TX, Fenarimol [60168-88-9]+TX, Nuarimol [63284-71-9]+TX,Bupirimate [41483-43-6]+TX, Dimethirimol [5221-53-4]+TX, Ethirimol[23947-60-6]+TX, Dodemorph [1593-77-7]+TX, Fenpropidine [67306-00-7]+TX,Fenpropimorph [67564-91-4]+TX, Spiroxamine [118134-30-8]+TX, Tridemorph[81412-43-3]+TX, Cyprodinil [121552-61-2]+TX, Mepanipyrim[110235-47-7]+TX, Pyrimethanil [53112-28-0]+TX, Fenpiclonil[74738-17-3]+TX, Fludioxonil [131341-86-1]+TX, Benalaxyl[71626-11-4]+TX, Furalaxyl[57646-30-7]+TX, Metalaxyl [57837-19-1]+TX,R-Metalaxyl [70630-17-0]+TX, Ofurace [58810-48-3]+TX, Oxadixyl[77732-09-3]+TX, Benomyl [17804-35-2]+TX, Carbendazim [10605-21-7]+TX,Debacarb [62732-91-6]+TX, Fuberidazole [3878-19-1]+TX, Thiabendazole[148-79-8]+TX, Chlozolinate [84332-86-5]+TX, Dichlozoline[24201-58-9]+TX, Iprodione [36734-19-7]+TX, Myclozoline [54864-61-8]+TX,Procymidone [32809-16-8]+TX, Vinclozoline [50471-44-8]+TX, Boscalid[188425-85-6]+TX, Carboxin [5234-68-4]+TX, Fenfuram [24691-80-3]+TX,Flutolanil [66332-96-5]+TX, Mepronil [55814-41-0]+TX, Oxycarboxin[5259-88-1]+TX, Penthiopyrad [183675-82-3]+TX, Thifluzamide[130000-40-7]+TX, Guazatine [108173-90-6]+TX, Dodine[2439-10-3][112-65-2] (freie Base)+TX, Iminoctadine [13516-27-3]+TX,Azoxystrobin [131860-33-8]+TX, Dimoxystrobin [149961-52-4]+TX,Enestroburin {Proc. BCPC+TX, Int. Congr.+TX, Glasgow+TX, 2003+TX, 1+TX,93}+TX, Fluoxastrobin [361377-29-9]+TX, Kresoxim-methyl[143390-89-0]+TX, Metominostrobin [133408-50-1]+TX, Trifloxystrobin[141517-21-7]+TX, Orysastrobin [248593-16-0]+TX, Picoxystrobin[117428-22-5]+TX, Pyraclostrobin [175013-18-0]+TX, Ferbam[14484-64-1]+TX, Mancozeb [8018-01-7]+TX, Maneb [12427-38-2]+TX, Metiram[9006-42-2]+TX, Propineb [12071-83-9]+TX, Thiram [137-26-8]+TX, Zineb[12122-67-7]+TX, Ziram [137-30-4]+TX, Captafol [2425-06-1]+TX, Captan[133-06-2]+TX, Dichlofluanid [1085-98-9]+TX, Fluoroimide[41205-21-4]+TX, Folpet [133-07-3]+TX, Tolylfluanid [731-27-1]+TX,Bordeaux Mixture [8011-63-0]+TX, Copperhydroxid [20427-59-2]+TX,Copperoxychlorid [1332-40-7]+TX, Coppersulfat [7758-98-7]+TX, Copperoxid[1317-39-1]+TX, Mancopper [53988-93-5]+TX, Oxine-copper [10380-28-6]+TX,Dinocap [131-72-6]+TX, Nitrothal-isopropyl [10552-74-6]+TX, Edifenphos[17109-49-8]+TX, Iprobenphos [26087-47-8]+TX, Isoprothiolane[50512-35-1]+TX, Phosdiphen [36519-00-3]+TX, Pyrazophos [13457-18-6]+TX,Tolclofos-methyl [57018-04-9]+TX, Acibenzolar-S-methyl [135158-54-2]+TX,Anilazine [101-05-3]+TX, Benthiavalicarb [413615-35-7]+TX, Blasticidin-S[2079-00-7]+TX, Chinomethionat [2439-01-2]+TX, Chloroneb [2675-77-6]+TX,Chlorothalonil [1897-45-6]+TX, Cyflufenamid [180409-60-3]+TX, Cymoxanil[57966-95-7]+TX, Dichlone [117-80-6]+TX, Diclocymet [139920-32-4]+TX,Diclomezine [62865-36-5]+TX, Dicloran [99-30-9]+TX, Diethofencarb[87130-20-9]+TX, Dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph)[211867-47-9]+TX, Dithianon [3347-22-6]+TX, Ethaboxam [162650-77-3]+TX,Etridiazole [2593-15-9]+TX, Famoxadone [131807-57-3]+TX, Fenamidone[161326-34-7]+TX, Fenoxanil [115852-48-7]+TX, Fentin [668-34-8]+TX,Ferimzone [89269-64-7]+TX, Fluazinam [79622-59-6]+TX, Fluopicolide[239110-15-7]+TX, Flusulfamide [106917-52-6]+TX, Fenhexamid[126833-17-8]+TX, Fosetyl-aluminium [39148-24-8]+TX, Hymexazol[10004-44-1]+TX, Iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, Kasugamycin [6980-18-3]+TX, Methasulfocarb[66952-49-6]+TX, Metrafenone [220899-03-6]+TX, Pencycuron[66063-05-6]+TX, Phthalide [27355-22-2]+TX, Polyoxins [11113-80-7]+TX,Probenazole [27605-76-1]+TX, Propamocarb [25606-41-1]+TX, Proquinazid[189278-12-4]+TX, Pyroquilon [57369-32-1]+TX, Quinoxyfen[124495-18-7]+TX, Quintozene [82-68-8]+TX, Schwefel [7704-34-9]+TX,Tiadinil [223580-51-6]+TX, Triazoxide [72459-58-6]+TX, Tricyclazole[41814-78-2]+TX, Triforine [26644-46-2]+TX, Validamycin [37248-47-8]+TX,Zoxamide (RH7281) [156052-68-5]+TX, Mandipropamid [374726-62-2]+TX,the compound of formula F-1

wherein Ra₅ is trifluoromethyl or difluoromethyl (W02004/058723)+TX,;the compound of formula F-2

wherein Ra₆ is trifluoromethyl or difluoromethyl (W02004/058723)+TX,;the racemic compound of formula F-3 (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl (W02004/035589)+TX, theracemic mixture of formula F-4 (anti)

wherein Ra₇ is trifluoromethyl or difluoromethyl (W02004/035589)+TX, thecompound of formula F-5

which is an epimeric mixture of racemic compounds of formulae F-3 (syn)and F-4 (anti), wherein the ratio from racemic compounds of formula F-3(syn) to racemic cmpounds of formula F-4 (anti) is from 1000:1 to 1:1000and wherein Ra₇ is trifluoromethyl or difluoromethyl (W02004/035589)+TX,the compound of formula F-6

wherein Ra₈ is trifluoromethyl or difluoromethyl (W02004/035589)+TX, theracemic compound of formula F-7 (trans)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, theracemic compound of formula F-8 (cis)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, thecompound of formula F-9

which is a mixture of the racemic compounds of formulae F-7 (trans) andF-8 (cis), wherein the ratio of the racemic compound of formula F-7(trans) to the racemic compound of formula F-8 (cis) is 2:1 to 100:1;and wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX,

the compound of formula F-10

wherein R₁₀ is trifluoromethyl or difluoromethyl (W02004/058723)+TX, theracemic compound of formula F-11 (trans)

wherein R₁₁, is trifluoromethyl or difluoromethyl (WO03/074491)+TX, theracemic compound of formula F-12 (cis)

wherein R₁₁ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, thecompound of formula F-13

which is a racemic mixture of formulae F-11 (trans) and F-12 (cis), andwherein R₁₁ is trifluoromethyl or difluoromethyl (WO 03/074491)+TX, andthe compound of formula F-14

(W02004/058723)+TX, and the compound of formula F-15

The active ingredient mixture of the compounds of formula I selectedfrom tables A and B with active ingredients described above comprises acompound selected from tables A and B and an active ingredient asdescribed above preferably in a mixing ratio of from 100:1 to 1:6000,especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to1:20, even more especially from 10:1 to 1:10, very especially from 5:1and 1:5, special preference being given to a ratio of from 2:1 to 1:2,and a ratio of from 4:1 to 2:1 being likewise preferred, above all in aratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750.Those mixing ratios are understood to include, on the one hand, ratiosby weight and also, on other hand, molar ratios.

The mixtures comprising a compound of formula I selected from tables Aand B and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromtables A and B and the active ingredients as described above is notessential for working the present invention.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. Thecompouds of formulae A-1 to A-26 are described in WO 03/015518 or in WO04/067528. The above described mixing partners are known. Where theactive ingredients are included in “The Pesticide Manual” [The PesticideManual-A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin;The British Crop Protection Council], they are described therein underthe entry number given in round brackets hereinabove for the particularcompound; for example, the compound “abamectin” is described under entrynumber (1). Where “[CCN]” is added hereinabove to the particularcompound, the compound in question is included in the “Compendium ofPesticide Common Names”, which is accessible on the internet [A. Wood;Compendium of Pesticide Common Names, Copyright© 1995-2004]; forexample, the compound “acetoprole” is described under the internetaddress http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “develoment code” isused or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

BIOLOGICAL EXAMPLES (%=Percent by Weight, Unless Otherwise Specified)Example B1 Activity Against Cydia pomonella

Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pickand are immersed in liquid paraffin (ca. 80° C.). After the paraffincoat has hardened, an aqueous emulsion containing 400 ppm of activeingredient is applied using a De Vilbis sprayer (25 ml, 1 bar). Afterthe spray coating has dried, the cubes are put into plastic containerswhich are then populated with two freshly hatched Cydia pomonella(1^(st) instar). The containers are then closed with a plastic cap.After 14 days incubation at 26° C. and 40-60% relative humidity, thesurvival rate of the caterpillars as well as their growth regulation isdetermined. In this test, compounds listed in Table C above show goodactivity. In particular compounds A.1.1, A.1.13, A.1.7 and A.1.4 have anactivity of over 80%.

Example B2 Activity Against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 larvae (2nd instar) of Diabrotica balteataand introduced into a plastic container. 6 days later, the percentagereduction in the population (% activity) is determined by comparing thenumber of dead larvae between the treated and untreated plants.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.1, A.1.4, B. 1.28, A.1.122 and A.1.7have an activity of over 80%.

Example B3 Activity against Heliothis virescens (foliar application)

Young soya plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (1st instar) of Heliothisvirescens and introduced into a plastic container. 6 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.4, A.1.1 and A.1.7 have an activity ofover 80%.

Example B4 Activity Against Heliothis virescens (Application to Eggs)

Heliothis virescens eggs, which have been deposited on cotton, aresprayed with an aqueous emulsion spray mixture comprising 400 ppm ofactive ingredient. After 8 days, the percentage hatching rate of theeggs and the survival rate of the caterpillars (% activity) areevaluated in comparison with untreated control batches.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.1, A.1.4, B. 1.28, A.1.122, A.1.57,A.1.131 and A.1.7 have an activity of over 80%.

Example B5 Activity Against Myzus Persicae (Foliar Application)

Pea seedlings are infected with Myzus persicae, subsequently sprayedwith a spray mixture comprising 400 ppm of active ingredient and thenincubated at 20°. 3 and 6 days later, the percentage reduction in thepopulation (% activity) is determined by comparing the number of deadaphids between the treated and untreated plants.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.4, A.1.122 and A.1.7 have an activityof over 80%.

Example B6 Activity Against Myzus persicae (Systemic Application)

Pea seedlings are infected with Myzus persicae, and their roots aresubsequently placed into a spray mixture comprising 400 ppm of activeingredient. The seedlings are then incubated at 20°. 3 and 6 days later,the percentage reduction in the population (% activity) is determined bycomparing the number of dead aphids between the treated and untreatedplants. In this test, compounds listed in Table C above show goodactivity. In particular compounds A.1.4, A.1.122 and A.1.7 have anactivity of over 80%.

Example B7 Activity Against Plutella xylostella

Young cabbage plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (3rd instar) of Plutellaxylostella and introduced into a plastic container. 3 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.1, A.1.4, B. 1.28, A.1.122, A.1.57,A.1.131, A.1.134 and A.1.7 have an activity of over 80%.

Example B8 Activity Against Spodoptera littoralis

Young soya plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (1st instar) of Spodopteralittoralis and introduced into a plastic container. 3 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in Table C above show good activity. Inparticular compounds A.1.13, A.1.1, A.1.4, B. 1.28, A.1.122, A.1.57,A.1.131 and A.1.7 have an activity of over 80%.

Example B9 Systemic Insecticide Test for Spodoptera littoralis (CottonLeafworm)

Four day old maize seedlings (Zea mais, variety Stoneville) are placedindividual in vials containing 24 ml water into which the chemical isdiluted at 12.5 ppm. Seedlings are allowed to grow for six days.Subsequently leaves are cut and placed in a Petri dish (5 cm diameter),inoculated with twelve to fifteen 1st instar S. littoralis larvae andincubated for four days in a growth chamber (25° C., 50% r.h., 18:6 L:Dphoto period). Number of alive insects are counted and percentage ofdead calculated. Tests were conducted with one replicate. In this test,compounds listed in Table C above show good activity. In particularcompounds A.1.13, A.1.1, A.1.4, A.1.7, A.1.13, A.1.122, A.1.131 andB1.28 have an activity of over 80%.

Example B10 Activity Against Frankliniella occidentalis

Bean leaf discs on agar in petri dishes or bean plants in a spraychamber are treated with diluted test solutions. After drying leaf discsare cut and placed in plastic cups on the surface of an agar layer andinfested with mixed population. 6 days (leaf discs) or 14 days (plants)after the infestation, samples are checked for reduction of treatedpopulation and compared to the non treated population. In this test,compounds listed in Table C above show good activity. In particularcompounds A.1.1, A.1.4, A.1.13, A.1.122 and A.1.7 have an activity ofover 80%.

1. A compound of formula I

wherein each of E and Z, which may be the same or different, representsoxygen or sulfur; A is C₁-C₆alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene,or a bivalent three- to ten-membered monocyclic or fused bicyclic ringsystem which can be partially saturated or fully saturated and cancontain 1 to 4 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, it not being possible for each ring systemto contain more than 2 oxygen atoms and more than 2 sulfur atoms; and itbeing possible for the three- to ten-membered ring system itself andalso for the C₁-C₆alkylene, C₂-C₆alkenylene and C₂-C₆alkynylene groupsto be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl, or by a three- toten-membered monocyclic or fused bicyclic ring system which can bearomatic, partially saturated or fully saturated and can contain 1 to 4hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, it not being possible for each ring system to contain more than2 oxygen atoms and more than 2 sulfur atoms, and it being possible forthe three- to ten-membered ring system itself to be mono-, di- ortrisubstituted by halogen, cyano, nitro, hydroxy, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl,C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen; X is oxygen, NH or C₁-C₄alkyl-N; Y is a three- toten-membered monocyclic or fused bicyclic ring system which can bepartially saturated or fully saturated and can contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur,it not being possible for each ring system to contain more than 2 oxygenatoms and more than 2 sulfur atoms; and it being possible for the three-to ten-membered ring system itself to be mono-, di- or trisubstituted byhalogen, cyano, nitro, hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl,C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl,C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino,C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy orC₃-C₆trialkylsilyl, or by a three- to ten-membered monocyclic or fusedbicyclic ring system which can be aromatic, partially saturated or fullysaturated and can contain 1 to 4 hetero atoms selected from the groupconsisting of nitrogen, oxygen and sulfur, it not being possible foreach ring system to contain more than 2 oxygen atoms and more than 2sulfur atoms, and it being possible for the three- to ten-membered ringsystem itself to be mono-, di- or trisubstituted by halogen, cyano,nitro, hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C₄alkoxycarbonyl-C₁-C₃-alkylthio, cyano-C₁ -C₃alkylthio,C-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,N,N-di(C₁-C₂alkyl)amino-sulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen; p is 0 or 1; q is 0 or 1; B is a three- tofour-membered ring system which is fully or partially saturated and cancontain a hetero atom selected from the group consisting of nitrogen,oxygen and sulfur, and it being possible for the three- to four-memberedring system itself to be mono-, di- or trisubstituted by halogen, cyano,nitro, hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-C₆haloalkyl,C₂-C_(haloalkenyl, C) ₂-C₆haloalkynyl, C₃-C₆halocycloalkyl,C₅-C₇halocycloalkenyl, C₅-C₈halocycloalkynyl, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino,C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy,C₃-C₆trialkylsilyl, or by a three- to ten-membered monocyclic or fusedbicyclic ring system which can be aromatic, partially saturated or fullysaturated and can contain 1 to 4 hetero atoms selected from the groupconsisting of nitrogen, oxygen and sulfur, it not being possible foreach ring system to contain more than 2 oxygen atoms and more than 2sulfur atoms, and it being possible for the three- to ten-membered ringsystem itself to be mono-, di- or trisubstituted by halogen, cyano,nitro, hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₇cycloalkenyl, C₅-C₈cycloalkynyl, C₁-₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₅-C₇halocycloalkenyl,C₅-C₈halocycloalkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy, C₃-C₆trialkylsilyl or phenyl, it beingpossible for the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio,C₁-C₃alkoxy-C₁-C₃alkylthio, C₂-C₄alkylcarbonyl-C₁-C₃alkylthio,C₂-C_(hd 4)alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano ornitro; and substituents at nitrogen atoms in the ring systems beingother than halogen; each R₁independently is halogen, nitro, cyano,hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C_(3-C)₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl,C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy,C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl, phenyl, benzyl orphenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted byhalogen, cyano, nitro, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C_(3-C)₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy orC₃-C₆trialkylsilyl; n is 0, 1, 2 or 3; each of R₂ and R₃, which may bethe same or different, represents hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl or C₃-C₈cycloalkyl; or C₁-C₆alkyl, C₂-C₆alkenyl,C₂-C_(6 alkynyl or C) ₃-C₈cycloalkyl substituted by one or moresubstituents selected from halogen nitro, cyano, hydroxy, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,C₃-C₆cycloalkylamino and C₁-C₆alkyl-C₃-C₆cycloalkylamino; D is phenyl,2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridyl or4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy,C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; orD is a group

R₄, R₄′, R₁₀, R₁₇, and R₁₉ independently from each other, are hydrogen,C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; R₅, R₆, R₈, R₁₁, R₁₂,R₁₅, R₁₆ and R₁₈ independently from each other, are C₁-C₆alkyl, orC₁-C₆alkyl mono-, di- or trisubstituted by halogen, cyano, nitro,hydroxy, C₁-C₄alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,C₂-C₄dialkylamino or C₃-C₆cycloalkylamino; or are phenyl, 2-pyridyl,3-pyridyl, 4-pyridyl; or are or phenyl, 2-pyridyl, 3-pyridyl or4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy,C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;R₇, R₉, R₁₃ and R₁₄ independently from each other, are hydrogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkenylor C₃-C₆haloalkenyl and agronomically acceptablesalts/isomers/enantiomers/tautomers/N-oxides of those compounds.
 2. Acompound according to claim 1, wherein R₄′ is hydrogen.
 3. A pesticidalcomposition, which comprises at least one compound according to claim 1of the formula I or, where appropriate, a tautomer thereof, in each casein free form or in agrochemically utilizable salt form, as activeingredient and at least one auxiliary.
 4. A composition according toclaim 3 for controlling insects or representatives of the order Acarina.5. A method for controlling pests, which comprises applying acomposition according to claim 3 to the pests or their environment.
 6. Amethod according to claim 5 for controlling insects or representativesof the order Acarina.
 7. A method according to claim 5 for theprotection of plant propagation material from the attack by pests, whichcomprises treating the propagation material or the site, where thepropagation material is planted.
 8. Plant propagation material treatedin accordance with the method described in claim
 7. 9. A process for thepreparation of a compound of formula I according to claim 1 or, whereappropriate, a tautomer thereof, in each case in free form or in saltform, which comprises a) for the preparation of a compound of formula I,in which R₂ is hydrogen and E and Z are oxygen, or, where appropriate, atautomer and/or salt thereof, reacting a compound of the formula

in which R₁, n, and D have the meanings given for the formula I, or,where appropriate, a tautomer and/or salt thereof with a compound of theformulaHN(R₃)-(A)_(q)-(X)_(p)—Y—B   (III), in which R₃, p, q, A, X, Y and Bhave the meanings given for the formula I, or, where appropriate, with atautomer and/or salt thereof or, b) for the preparation of a compound offormula I, or, where appropriate, a tautomer and/or salt thereof,reacting a compound of the formula

in which R₁, R₂, n, Z and D have the meanings given for the formula I;and X₁ is a leaving group,or, where appropriate, a tautomer and/or saltthereof with a compound of the formulaHN(R₃)-(A)_(q)-(X)_(p)—Y—B   (III), in which R₃, p, q, A, X, Y and Bhave the meanings given for the formula I, or, where appropriate, with atautomer and/or salt thereof or, c) for the preparation of a compound offormula I, or, where appropriate, a tautomer and/or salt thereof,reacting a compound of the formula

in which R₁, R₂, R₃, n, p, q, A, X, Y, Z and B have the meanings givenfor the formula I, or, where appropriate, a tautomer and/or salt thereofwith a compound of the formulaX₂C(═O)D   (VI), in which R₁has the meaning given for the formula I; andX₂ is a leaving group, or, where appropriate, with a tautomer and/orsalt thereof.
 10. A compound of the formula

in which R₁, R₂, R₃, n, p, q, A, X, Y, Z and B have the meanings givenfor the formula I in claim
 1. 11. A compound according to claim 10,wherein R₁ is C₁-C₄alkyl, halogen, C₁-C₅haloalkyl, nitro, C₁-C₄alkoxy,C₁-C₄-haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl; R₂ and R₃ are hydrogen; A is C₁-C₆alkylene whichmay be substituted by C₃-C₆cycloalkyl, C₂-C₆alkenyl, cyano,C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₁-C₄alkoxy, halogen orC₁-C₆haloalkyl; or A is C₃-C₆cycloalkylene; p and q are, independentlyfrom each other, 0 or 1; X is oxygen, NH; NCH₃ or NC₂H₅; Y isC₁-C₄alkylene, C₂-C₆alkenylene or C₃-C₆alkinylene or, C₁-C₄alkylene,C₂-C₆alkenylene or C₃-C₆alkinylene substituted by halogen,C₃-C₆cycloalkyl, C₁-alkysulfonyl or C₁-C₄-alkoxy; and B is cyclopropylor cyclobutyl which may be mono- di-, or trisubstituted by halogen,C₁-C₄alkyl, hydroxy, cyano, C₁-C₄alkoxy or C₁-C₄alkylthio; or B isCH(CH₂O), CH(CHMeO), CH—(CMe₂O), CH(CH₂S), CH(CH₂OCH₂), CH(CHMeOCH₂),CH(CMe₂OCH₂), CH(CH₂S—(O)₂CH₂), CH(CHMeS(O)₂CH₂), CH(CMe₂S(O)₂CH₂),C(Me)-(CH₂O), C(Me)(CHMeO), C(Me)-(CMe₂O), C(Me)-(CH₂S),C(Me)-(CH₂OCH₂), C(Me)(CHMeOCH₂), C(Me)-(CMe₂OCH₂), C(Me)-(CH₂S(O)₂CH₂),C(Me)-(CHMe-S(O)₂CH₂) or C(Me)-(CMe₂-S(O)₂CH₂).
 12. A compound accordingto claim 11, wherein B is cyclopropyl or cyclobutyl which may be mono-di-, or trisubstituted by halogen, C₁-C₄alkyl, hydroxy, cyano,C₁-C₄alkoxy or C₁-C₄alkylthio.
 13. A compound of the formula

in which R₁, n, and D have the meanings given for the formula I in claim1.